43. No. 2. pp. 269-278. ,988. 0009-2509/E@ $3.00+0.

00
0 1988 Pergamon Journals Ltd.

ON THE DANGERS OF “TUNING” EQUATION OF STATE

PARAMETERS

KAREN SCHOU PEDERSEN,+ PER THOMASSENt and AAGE FREDENSLUNDB

+CALSEP A/S, Lyngby Hovedgade 29, DK-2800 Lyngby, Denmark; ZSTATOIL, N-4001 Stavanger,
Norway; 4Instituttet for Kemiteknik, Technical University of Denmark, DK-2800 Lyngby, Denmark

(Received 2 February 1987; in revised form 28 June 1987; accepted 9 July 1987)

Abstract-Equations of state (EOS) are widely used in phase equilibrium calculations for mixtures
containing undefined, heavy hydrocarbons. “Tuning” to measured P VT data is commonly used to find EOS
parameters describing the thermodynamic properties of the mixtures in question. It is shown that “tuning” is
unnecessary if the composition of the oil is properly described on the basis of an experimental compositional
analysis and a newly developed characterization procedure. It is found that using EOS parameters “tuned” to
one specific property yields unreliable predictions of other thermodynamic properties.

1. INTRODUCTION Pedersen et al. (1984a,b, 1985) have presented a purely

Equations of state (EOS) used in phase
are widely
equilibrium calculations for mixtures containing un-
defined, heavy hydrocarbons. “Tuning” to measured
dew and bubble points and PVT data (constant
volume depletion data, differential liberation data, etc.)
is commonly used to find EOS parameters for describ-
ing the properties of the mixtures in question. In
practice, only a limited number of P VT measurements
are carried out for a given mixture. A description of the
commonly performed PVT experiments is given by
Pedersen et al. (1984b).
It is of utmost importance that the equation of state
yields reliable predictions for a large number of
different properties (densities, enthalpies, K values,
etc.). In addition, the EOS must furnish reliable
predictions over a wide range of not only pressure and
temperature, but also composition. The importance of
this point may be illustrated by a few practical
situations:
(a) the mixtures produced undergo a number of
process steps at various levels of temperature and
pressure;
(b) mixtures of hydrocarbons from different fields
may be mixed and further processed; and
(c) reinjection of gas may be used and will often result
in a reservoir fIuid of near-critical composition.
There is no a priori reason to believe that EOS
parameters “tuned”, for example, to PVT data at one
composition in a limited pressure and teFperature
region will lead to improved predictions of enthalpies and
K values at other temperatures, pressures and
compositions. More likely than not, the predictions
will be worse due to (1) experimental errors in the
compositional and other experimental data to which
the parameters are “tuned” and (2) model im-
perfections.
It is necessary that the EOS parameters for a given
component or pseudo-component are valid for a wide
range of temperatures, pressures and compositions.
269
predictive procedure for the determination of EOS
parameters of mixtures containing undefined, heavy
hydrocarbons. The procedure is based on the
Soave-Redlich-Kwong (SRK) equation of state
(Soave, 1972) and uses binary interaction parameters,
k,,, equal to zero for all hydrocarbon-hydrocarbon
interactions, while non-zero values may be used for
interactions with non-hydrocarbons.
A prerequisite for successful application of charac-
terization is accurate and comprehensive analytical
data. The calculated results for the PVTproperties, for
example, are sensitive to even minor differences in the
reported analytical data, in particular those concerning
the heavy fractions. Even very small amounts of
components as heavy as CsO may appreciably influence
some properties of the reservoir fluids. Most analytical
techniques applied to complex petroleum mixtures are
unable to provide details about components as heavy
as that. Distillation at reduced pressure permits hydro-
carbon analyses up to about C,,. Hollow tube gas
chromatography may yield analyses up to about Ca5.
For the residue, however, information is obtained only
on the average molecular weight, the specific gravity
and the PNA distribution. The detailed composition
must be estimated. It is therefore important that the
reported analytical data provide the best possible basis
for estimating the molar distribution and the com-
ponent properties of the residue by extrapolation.
2. COMPOSITIONAL ANALYSES
The reservoir fluid samples which are analysed in the
laboratory are either bottom hole sample-s or samples
of the gas and liquid streams from a well-head
separator.
The analytical data of this work and those reported
by Pedersen et al. (1984a,b, 1985) were measured by
STATOIL. The analytical techniques are briefly de-
scribed below.
Bottom hole samples are flashed in the laboratory to
standard conditions (i.e. 1 atm and 15°C). The gas and
270 KAREN SCHOU PEDERSEN et al.

liquid phases are analysed separately and the reservoir
fluid composition is calculated from the measured
gas/liquid ratio.
The gas and liquid samples from a separator are
both flashed to standard conditions. The two gas
phases and the combined liquid phase are analysed
separately. Gas chromatographic (GC) analyses are
used to analyse the gas phases (Osjord and Malthe-
S@renssen, 1983) and the lighter components of the
liquid phase. Using mass spectroscopy as a sup-
plementary technique, all the components Nz, CO*
and C,-C, can be quantitatively identified. It is
generally not possible to make component analyses for
the heavier components. In case the C,,, fraction is
not analysed further, the determination of the molecu-
lar weight (M W) and molar fraction of the C1 o +
fraction must be based on a measurement of the MW
of the total liquid phase at standard conditions. A
commonly used analytical technique for oil samples is
a true boiling point distillation (TBP) process by which
the heavy hydrocarbons are split in boiling point
fractions. The distillation equipment used at
STATOIL permits boiling point fractions as heavy as
C,, to be distilled off. For each fraction, measurements
may be performed of density, MW and PNA distri-
bution (Osjord et al., 1985). The composition resulting
from GC and TBP analyses is expressed in wt %. In
order to convert it to mol%, the MW of each
component and TBP fraction must be known. For the
well-defined components this is problem-free. For the
boiling point fractions, the accuracy of the final molar
composition depends on the accuracy of the measured
MW. At STATOIL, the MWs of the C7 + fractions are
determined by measuring the freezing point depression
of a solution of the given fraction in benzene.
Measurements of the molecular weight are per-
formed on the total C,,, fraction and the TBP
residue, in addition to the measurements of the MWs
of the TBP fractions. The measured average MWs and
composition allow the consistency of the MWs to be
checked by material balances.
A TBP fraction may be split into saturated (paraf-
fins + naphthenes) and unsaturated (aromatics) com-
pounds using liquid-liquid chromatography. This is a
preparative analytical technique, e.g. sufficient
amounts of each subfraction are produced to allow
measurements of physical properties such as density
and MW.
In an appendix-not included, but available from
the authors (K.S.P.banalytical data are given for oil
mixtures (oils A and B) and for two gas condensate
mixtures (gc A and gc B). The data include com-
positions, PNA distributions, TBP data and MWs. In
the following, these data are used in a comparison of
predictive characterization methods. First, the total
data set will be used, and then deficient data sets
(lacking data or less accurate data) will be used
together with different “tuning” procedures. Hereby
the consequences of commonly used approximate
simulation procedures may be studied.
3. SIMULATION OF PYT PROPERTIES WITH AND
WITHOUT “TUNING”
First, we will study a typical North Sea oil, oil A, for
which ample analytical information is available. A
differential liberation experiment was simulated using
the characterization procedure of Pedersen et al. The
procedure is described briefly in Appendix A. The
hydrocarbons of the mixtures are represented using 6
and 20 hydrocarbon fractions, respectively. The results
of the characterization using 6 hydrocarbon fractions
are shown in Table 1. Table 2 shows the results for the
measured bubble points and the predicted values using
6 and 20 hydrocarbon fractions, respectively. Figure 1
shows measured and calculated oil densities. The
procedure of Peneloux and Freze (1982) was used to
calculate the oil densities. Peneloux’s c parameters of
the C,, fractions are here found from the following
equation:
c = 0.597 MW”.686 (1)
where MW is the molecular weight and c is expressed
in cm3/mol.
As described by Michelsen (1986), the computation
time of flash calculations can be considerabIy reduced
if k, values equal to zero are used for all interactions.
Bubble points calculated for oil A using kij values equal
to zero for all interactions are also shown in Table 2.
The results of the predictive procedure shown in Fig.
1 and Table 2 exhibit satisfactory agreement between
experimental and calculated values, a typical result for

Table 1. Results of the characterization procedure for North Sea oil A using six
fractions to represent the hydrocarbons

=c Acentric
No. Component Mol y0 (at@ factor

: 0.12
0.69 304.20
126.20 72.80
33.50 0.0400
0.2250
3 CI 47.04 190.60 45.40 0.0080
4 C, 10.08 339.59 44.86 0.1267
5 CL-6 8.20 464.36 33.25 0.2415
6 C?-12 19.50 598.72 26.8 1 0.5641
c,,-2, 10.13 733.79 16.18 1.0214
G-.30 4.25 895.75 10.15 1.6313
 “Tuning” EOS parameters 271

Table 2. Measured and calculated bubble points of North oil mixtures with only a small content of non-
Sea oil A at T = 72.8”C hydrocarbons.
We now show the effect of adjusting the MW of a
Pressure
%DeV+ plus fraction.
(bar)
Figure 2 shows measured and simulated liquid
Experimental bubble point 238.0 - dropout curves for a constant mass expansion exper-
Calculated using 20 CH fractions iment on gc A. Simulated results are shown based on
(some k,is different from zero) 234.6 - 1.4
Calculated using 6 CH fractions
the composition analysis up to CIO + and based on the
(some k,s different from zero) 238.3 -0.1 analysis up to Cs 2 +. Also shown in Fig. 2 are results for
Calculated using 20 CH fractions the liquid dropout curves assuming the MW which is
(all k,s equal to zero) 233.2 - 2.0 measured for the total liquid phase at standard
Calculated using 6 CH fractions
conditions and assuming MWs which deviate by + 5 o/O
(all k,s equal to zero) 236.9 - 0.5
and - 5 o/Ofrom this value. The results are influenced
t %Dev = (measured value - experimental value) by the MW because the critical parameters (T,, P,and
x lOO/measured value. o) calculated during the Cl+ characterization pro-

200 300
Pressure, bar

Fig. 1. Measured and calculated densities for North Sea oil A at T = 72.8”C. -, Experiment; - - -, 20 CH
fractions; - . -, 6 CH fractions.

400 500
Pressure, bar

Fig. 2. Constant mass expansion data at T = lll.l”C for gas condensate A. - Experimental results;
- - -, standard characterization (C,,, ), --, standard characterization (C ,e+); :.--.-, MW of total
liquid sample; - - - -, MW of total liquid sample + 5 %; - - - - - -, M W of total liquid sample - 5 %.
272 KAREN SCHOU PEDERSEN et al.

cedure depend on this property. The procedure of We will now study in somewhat greater detail oil
Peneloux and Freze (1982) was used to calculate the mixture B (oil B) for which measured and calculated
phase densities. It is seen that changing the MW to bubble points are shown in Table 5. Six hydrocarbon
obtain better liquid dropout curves results in poorer fractions were used in the calculations to represent the
dew point predictions. hydrocarbon constituents of the oil mixture.
The amount ofanalytical information available for a Calculated results are shown based on the measured
given petroleum mixture is often less complete than is C 1,, + M W and using C1 ,, + M Ws which deviate + 10 0/O
the case for oil A and gc A. Table 3 shows limited
analytical data for a third oil mixture oil C. It will be
shown below that the standard, purely predictive Table 3. Molar composition of North Sea oil C
characterization procedure of Pedersen et al. may also
be applied with satisfactory results to this less exten- Specific
Component M 01 ‘yO MW gravity
sively described mixture. Gas with the composition
listed in Table 4 was added to the oil, and the bubble N2 0.31
point of the resulting mixture was determined. More COZ 0.69
gas was subsequently added, and the new bubble point G 47.69
G 6.64
was measured. The addition of gas was continued until
G 4.59
the saturation point at the given temperature changed iCo 0.85
to a dew point. The addition of gas was simulated and nG 1.74
the resulting saturation points were calculated using iC, 0.70
the purely predictive characterization procedure of nG 0.46
G 1.69
Pedersen et al. A total of six hydrocarbon fractions
C 7+ 34.64 234.0 0.8688
were used to represent the oil + gas mixtures.
Experimental and simulated results are shown graphi-
cally in Fig. 3.
A different characterization procedure was also
tried. The measured MW of the C, + fraction of the oil Table 4. Molar composition
is 234.0, which roughly corresponds to that of a C,, of the gas which was added
to North Sea oil C
fraction. If the properties of Cl7 (Reid et al., 1977) are
used to represent those of the total C, + fraction, the Component Mol “/,
bubble point pressure is calculated to be 34.1 “/, lower
than the measured value. If a binary interaction N* 0.55
coefficient of 0.145 is assumed for the interaction CO2 1.43
C, 81.63
between methane and the C,, fraction having the G 10.12
properties of C1 ,, a perfect match of the measured C3 5.20
bubble point of the original oil is achieved. However, iC, 1.06
as is shown in Fig. 3, the estimated saturation points of nG 0.0 1
the oil + gas mixtures are in this case very different
from the experimental values.

/
/I
/// /Dew Point
/

0 0.5 1.0

Molar Fraction of Gas Added par Mole Oil

Fig. 3. Experimental and calculated saturation points at T = 11 l.l”C for mixtures of North Sea oil C and the
gas shown in Table 4. 0, Experimental saturation points (bubble points where nothing is indicated); -,
standard characterization; - - - -, “tuned” properties.
 “Tuning” EOS parameters 273

Table 5. Measured and calculated bubble points of oil B at T = 74.5”C

Pressure
(bar) “/,Dev+

Exnerimental bubble noint 235.0

Calculated bubble point based on
measured C,,, MW 233.4 - 0.6
Calculated bubble point based on
measured C, 0 + MW raised by 10% 233.3 - 0.7
Calculated bubble point based on
measured C I e + MW lowered by 10% 235.4 0.2
Calculated bubble point baaed on com-
position with erroneous GOR 214.5 - 8.7
Calculated bubble point based on com-
position with erroneous GOR using kzj
values different from zero 235.0 0.0

+%Dev defined as in Table 2.

and - 10 “/0 from the measured value. The same molar
fraction of C,,, was used in all three cases. The
composition of oil B is based on compositions and
amounts measured for the gas-liquid phases resulting
from a single stage gash to standard conditions. Also
shown in Table 5 is the calculated bubble point of a
mixture where the gas and liquid phases were com-
bined using a gas/oil ratio 5 “/, lower than the measured
ratio. “Tuning” to the measured bubble point was
used for this erroneous composition. Hydro-
carbon-hydrocarbon kij values which depend slightly
on the ratio of the MW of the constituent components
in the following manner were introduced:
MW,
kij = 0.00145 -MW, for MWi > MW, (2)
J the methane concentration at the various depletion
MW.
kij = 0.00145 2 for MW, > MW,. (3)
MWi
In this case, perfect agreement with the measured
bubble point was obtained (see Table 5). A three-stage
separation process was carried out in the laboratory on
oil B. The results are summarized in Tables 6 and 7.
Simulated results are shown using the standard charac-
terization procedure together with (1) the measured
C iO+ MW, (2) a Clot M W which is 10 y0 higher than
the measured value, and (3) a C,,, + MW which is 10 y0
lower than the measured value. The same Clo+ molar
fraction was used in all cases. The results are seen to be
very sensitive to the Cl,,+ MW.
Also shown are the simulated results for the com-
position with a gas/oil ratio which is 5 “/, lower than
what was measured. Results are shown using
hydrocarbon-hydrocarbon interaction parameters
equal to zero (column 4) and determined from eqs (2)
and (3) (column 5). No improvement over k, = 0 was
obtained by tuning to the measured bubble point.
Results of a constant volume depletion experiment
are available for gas condensate B (gc B). This is a
heavy gas condensate which at pressures > 2OObar and
under the conditions of the depletion experiment has
almost identical gas and liquid phases. Thus it exhibits
near-critical behaviour. The problems of using a cubic
equation of state in the near-critical region are re-
flected in the deviation between the measured and
calculated liquid dropout curves using the standard
characterization procedure. The data used to represent
the C, + fraction are presented in Table 8. No grouping
was made of the lighter components. In order to obtain
better agreement with the liquid dropout curve,
“tuning” of T,, P, and w was attempted. Binary
interaction coefficients of zero were maintained for the
hydrocarbon-hydrocarbon interactions. The resulting
values for T,, P, and w of the C,, fractions are
presented in Table 9 and the “tuned” liquid dropout
curve is also shown in Fig. 4. The composition of the
gas removed at each depletion level was measured.
Figure 5 shows the measured and calculated results for
levels. In Fig. 6 are shown the measured and calculated
compressibility factors at the conditions of the de-
pletion experiment. The “tuned” predictions of Figs 5
and 6 are slightly inferior to the results using the
standard characterization procedure.
4. DISCUSSION
Naturally occurring oil and gas mixtures contain a
large number of components. A complete
different
component analysis will probably never be available,
and even if it were it might be difficult to predict the
mixture properties with a high degree of accuracy
because of the complexity of the mixtures and the
limitations of the model. It has long been the practice
to use measured PVTdata to estimate the properties of
heavy hydrocarbon fractions. This “tuning” to
measured PVT data may hide analytical deficiencies
such as the lack of a consistent procedure for measur-
ing the MWs of C,, fractions or errors in the
compositional analyses themselves. As previously re-
ported (Pedersen et al., 1984a,b, 1985), the saturation
points and phase properties can be predicted with
good accuracy when consistent analytical data are
available. Only the amount of the liquid phase of gas
condensates at pressures just below the dew point
pressure is somewhat overestimated. If the mentioned
 Table 6. Results for oil B of the separator test for gas oil ratios (GOR) (standard m3 of gas per standard m3 of oil)

Calc. GGR from measuredcomposition Calc. GOR from erroneous composition

‘A,,+ MW C,,, MW t 10% CIO+ MW-10% Std. Char. “Tuned” kij # 0

Separator Measured GOR GOR GOR GOR GOR

stage (& GOR (1) %Devt (2) %Dev (3) %Dev (4) %Dev (5) %Dev

1 68.9 41.2 90.2 87.7 -2.6 80.6 - 10.4 96.9 7.7 73.9 - 17.9 77.2 - 14.2
2 22.5 86.6 37.0 34.5 -6.8 32.3 - 12.7 37.0 0.0 32.2 - 13.0 29.9 - 19.2
3 1 15.0 13.6 13.1 - 3.7 12.2 - 10.3 14.2 4.4 12.6 - 7.4 12.2 - 10.3

+%Devdefinedas in Table 2.
(lb(s): Column numbers referred to in the text.

Table 7. Results for oil B of the separator test for oil formation factors (m3 of separator liquid per standard m3 of liquid)

Calc. Bo from measuredcomposition Calc. Bo from erroneous composition

C,,+ MW Cte+ MWtlO% C,,, MW-10% Std. Char. “Tuned” kij # 0

separator Measured Bo Bo Bo Bo Bo
me GOR (1) %Devt (2) %Dev (3) %Dev (4) %Dev (5) %Dev

1 235.0 74.5 1.389 1.352 -2.1 1.320 - 5.0 1.387 -0.1 1.306 - 6.0 1.308 - 5.8
2 68.9 41.2 1.147 1.117 - 2.6 1.105 - 3.7 1.127 - 1.7 1.109 - 3.3 1.102 - 3.9
3 22.5 86.6 1.105 1.065 - 3.6 1.056 - 4.4 1.071 -3.1 1.062 -3.9 1.061 -4.0

t %Devdefinedas in Table 2.
(l)-(5): Column numbers referred to in the text.
 “Tuning” EOS parameters 275
Table 8. Resultsof the standardcharacterizationof the C, + characterization procedure is used, six hydrocarbon
fraction of North Sea gas condensate B fractions are for many practical purposes sufficient to
represent the hydrocarbons of a petroleum mixture. kij
PC Acentric
No. Component factor values equal to zero may be used for all interactions if
Mol “/, (atm)
the mixtures do not contain more than a few per cent of
1 G--9 5.77 560.7 30.07 0.4327 non-hydrocarbons. The results presented in Table 2
2 Cl+IS 2.72 658.3 21.00 0.7479 and Figs 1 and 2 agree with these previously reported
3 C, T--60 1.48 802.3 12.16 1.2993
observations (Pedersen et al., 1984a,b, 1985).
Figure 2 shows how sensitive the results for the dew
point and the liquid fraction are to the M Ws of the plus
Table 9. Results of “tuned” characterization of the C,, fraction. The measured ClO+ MW and the C,,,, MW
fraction of North Sea gas condensate B which is calculated from the C,,-+& + MWs deviate
Acentric by 2.5%. This difference is reflected in a slight devi-
T, p,
No. Component Mol % (KI (atm) factor ation between the calculated liquid dropout curve
based on the analysis up to C, O+ and the one based on
1 CT--9 5.77 571.0 27.00 0.3000 the analysis up to CJz + _ Experimental inaccuracies in
2 c,o-c,, 2.72 629.0 21.00 0.6000
the determination of the MW of around 5 “/, are to be
3 c, ,-Go 1.48 782.0 14.50 1.3500
expected. Figure 2 shows that deviations of that order

100 200 300 -400

Pressure, bar

Fig. 4. Constant volume depletion experimentfor gas condensateC at T = 136.1-C. 0, Experiment;-,

standard characterization;- - - -, “tuned” properties.

65 I 1

0 200 300 400

Pressure, bar

Fig. 5. Experimentaland calculatedmethane composition correspondingto the constant volume depletion

experiment of Fig. 4. 0, Experiment;-, standard characterization;- - - -, “tuned” properties.
276 KAREN SCHOUPEDERSEN
0 100
Fig. 6. Measured and calculatedcompressibilityfactors correspondingto the constant volume depletion
experimentof Fig. 4. 0, Experiment;-, standard characterization;- - - -, “tuned” properties.
of magnitude influence the results for the simulated
liquid dropout curve considerably. Therefore accurate
predictions of dew points cannot be expected in the
case where the molar composition is based on the
measured MW of the total liquid phase resulting from
a flash to standard conditions.
Only data for the total C, + fraction are available for
oil C. Nevertheless, perfect agreement is obtained
between the measured bubble point and the one
predicted using the characterization procedure of
Pedersen et al. (1984a,b, 1985) (see Fig. 3). What is even
more interesting is that the saturation points of
mixtures of oil C and the gas of Table 4 are also
predicted with great accuracy. “Tuning” by means of
k,, values different from zero for the C,-C, + interac-
tions was tried for oil C. As seen from Fig. 3, the kij
values which were appropriate for the original oil give
saturation points from the oil + gas mixtures which
deviate considerably from the measured results.
The simulated bubble point of oil B is not very
sensitive to the C,,, MW (see Table 5) whereas the
separator gas/oil ratios and oil formation factors are
markedly influenced by this parameter, as seen from
Tables 6 and 7. This indicates that the transition from
the single-phase region to the two-phase region is
strongly influenced by the size of the heaviest mol-
ecules of the mixture, whereas the phase behaviour in
the two-phase region is less influenced by that par-
ameter. The results of Tables 6 and 7 also show that
erroneous data cannot be accounted for by tuning to a
measured bubble point using kii values different from
zero for hydrocarbon-hydrocarbon interactions.
These results indicate that even minor adjustments
of the standard characterization procedure may not be
used with confidence if the results are going to be used
for the prediction of properties other than the one to
which the data were “tuned”.
It is generally accepted that a large degree of
accuracy cannot be expected when cubic equations of
et al.
200 300 400
Pressure, bar
state are used for phase equilibrium calculations on
mixtures in the near-critical region. The deviation
between the measured and the predicted liquid
dropout curves for gas condensate B (see Fig. 4) is
therefore to be expected. The deviation may originate
either from inaccuracies in the calculated phase split or
from the calculation of the phase densities. The gas-
phase compressibility factor at each depletion level was
determined and the liberated gas was analysed. There
is good agreement between the measured and calcu-
lated gas-phase compressibility factors and compo-
sitions using the standard characterization, whereas
larger deviations are found for the results based on the
“tuned”characterization. This means that the *‘tuning”
has served only to improve the results for the liquid
volume which was used in the “tuning” process,
whereas less accurate results are obtained for other
thermodynamic properties.
5. CONCLUSlON
Predictions of phase equilibria and phase properties
of oil and gas mixtures satisfactory for many practical
purposes are possible using the SRK equation of state.
Accurate analytical data are required. In most cases, it
is sufficient to have an analysis up to C,, + . It is
important to have accurate measurements of the MWs
of the residues and hydrocarbon fractions, in par-
ticular for gas condensates. EOS parameters “tuned”
to one specific property are found to yield unreliable
predictions of other thermodynamic properties.
If the analytical data are inaccurate, “tuning” to
properties reported for these erroneous compositions
may lead to highly uncertain predictions.
The authors have, in principle, no qualmss about
“tuning” if the “tuning” procedure is carried out and
applied cautiously. This means that a proper par-
ameter sensitivity analysis must be performed relating
 “Tuning” EOS parameters 277

the sensitivity of the data to which the EOS is “tuned”
to the sensitivity of the desired predicted properties.
DEFINITIONS
Gas/oil ratio volume at standard conditions
of the combined gas from the
separators divided by the liquid
volume in the separator
dard conditions
Oil formation factor liquid volume in a given separ-
ator divided by the liquid
volume in the separator at stan-
dard conditions
Standard conditions temperature = 15°C; pressure
= latm
NOTATION
Pedersen, K. S., Thomassen, P. and Fredenslund.Aa., 1985,
Ind. Engng Chem. Proc. Des. Dev. 24, 948.
Peneloux, A. and Freze, R., 1982, Fluid Phase Equilibria 8,7.
Reid, R. C., Prausnitz, J. M. and Sherwood, T. K., 1977, The
Properties of Gases and Liquids. McGraw-Hiil, New York.
Soave, G., 1972, Chem. Engng Sci. 27, 1197.
APPENDIX A
at stan- (1) Recommended characterization procedure for the SRK
equation of state
The components of a reservoir fluid may be classified as
follows:
Defined componenrs for which there exists a quantitative
GC analysis and for which T,, P, and w are known.
TBP fractions covering the true boiling point fractions
between C, and CsO, each of which contains many different
components.
For the North Sea oils, the best results were obtained using
the Cavett (1964) relations for T, and P,:

SO oil formation factor (see Definitions) T, = 768.071+ 1.7134 T,, -0.10834 x 1O-2 T:,,
volume correction factor defined in eq. (1) +0.3889x 1O-6 7-:,-0.89213x 10-2T50API
L-I hydrocarbons
+0.53095 x 1O-6 T:,, API +0.32712
EOS equations of state x IO-’ T:,,API’ (Al)
GC gas chromatographic
gas/oil ratio (see Definitions) log,, P, = 2.829 +0.9412 x lo-” T,, -0.30475
GOR
gas condensate x 10-5T&,+0.15141 x lo-*T&,
gc
K equilibrium factor -0.20876 x 1O-4 TS,API +0.11048
kij binary interaction coefficient between com- x lo-‘T:,API+0.1395 x 10-9Z-:0AP12
ponent i and component j
- 0.4827 x 10-l T,, API’ (A2)
MW molecular weight
critical pressure and the Lee-Kesler relations (Kesler and Lee, 1976) for w:
P,

In P,,- 5.92714 +6.09648/T,,+ 1.28862 In T,,-0.169347 T&

W= (A31
15.2518 - 156875/T,,- 13.4721 In TBr+0.43577T&
(for T,, -z 0.8)

w = -7.905 +O.l352K -0.007465K’

+ 8.359 T,,+ (1.408 - O.O01063K)/T,, (A4)

(for T,, > 0.8).

PNA paraffin-naphthene-aromatics In eqs (Al) and (A2), API = 141.5/SG-131.5, where SG is

the 60”F/60”F specific gravity. The critical temperature, T,,
TBP true boiling point
and the mid-volume boiling point of the fraction,
T, critical temperature T 50, are given in “F and P, is in psia. In eqs (A3) and (A4),
w acentric factor T,, is the reduced boiling point, TufT,, and P,, is the
reduced pressure, Pu/P,, where Pu is the pressure at which
REFERENCES the boiling point, T,, was measured. K is the Watson
characterization factor, which equals Th13/SG, where Tn is in
Cavett, R. H., 1964, Physicaldata for distillationcalculations, “R and SG is as above.
vapor-iiquid equilibria, 27th Midyear Meeting, API The results are improved if the PNA distribution of each
Division of Refining, San Fransisco, CA, 15 May. boiling point fraction is taken into consideration in the
Katz, D. L. and Firoozabadi, A., 1978, J. Pet. Technol. 20, following manner:
1649.
Kesler, M. G. and Lee, B. I., 1976, Hydrocarbon Proc. 55, 153.
T, = XPT,P+~N~,N+ x~Tc~ (A51
Michelsen, M. L., 1986, Ind. Engng Chem. Proc. Des. Dev. 25,
184. p,= XPPcP+YNPcN+XAPcA (‘46)
Osjord, E. H. and Malthe-Sorenssen, D., 1983, J. Chromotogr.
w = xpop+x,w~+x*w~. (A7)
297, 219.
Osjord, E. H., Rdnningsen, H. P. and Tau, L., 1985,
x is the molar fraction and the subscripts P, N and A refer
Distribution of weight, density and molecular weight in
to the paraffin, naphthene and aromatic compounds,
crude oil derived from computerized capillary GC analysis, respectively.
6th International Symposium on Capillary Chro-
TRP residue. In the case of gas condensates, the molar
matography, Palazzo de1 Congressi, Riva del Garda, Italy,
composition of the TBP residue is estimated by assuming a
20-24 May.
logarithmic relationship between the molar content, xi_,, of a
Pedersen, K. S., Thomassen, P. and Fredenslund, Aa., 1984a,
fraction and the corresponding carbon number, C,, for C,
Jnd. Engng Chem. Proc. Des. Dev. 23, 163.
2 7:
Pedersen,K. S., Thomassen, P. and Fredenslund, Aa.. 1984b,
Ind. Engng Chem. Proc. Des. Dew 23, 566. CN=A,+B, InxB. (A8)
278 KARENSCHOUPEDERSEN~~ al.

A, and Bi are constants which are determined by a least- is used for the fractions heavier than I&. For the oils, the
squares fit to the experimental TBP data for the C,C3,, weight-based TBP curve is related to carbon number frac-
fractions. CgO is the heaviest carbon number fraction con- tions assuming 6 K boiling intervals per carbon number for
sidered, and molar fractions below 5 x 10e6 are neglected. If the Ca5+ fractions.
the measured TBP residue is larger than the one caiculated
from the obtained A, and B, values, A, and B, are changed (2) Reduction of the number of components
accordingly. A procedure was developed whereby all hydrocarbon
For the heavy oil systems, a different characterization segments of the C, + fractions are given approximately equal
procedure is used. importance. This is accomplished via a grouping of carbon
The TBP distillation curve is extrapolated to 100 wt “/, number fractions on weight basis. The total C, + fraction is
distilled off by fitting the fifth-degree polynomial to the divided into three (or more) groups, which on a weight basis
experimental TBP data plus the following two artificially are of approximately equal size. The group critical properties
generated data points: are computed as weight-mean average values:
T _,~ = IO-o.“‘27 Tsowtx/.‘.‘0,SG-o.6495
(A9)
TCi= xxjMWjTCi xxjMWj
T l_tx = ~0’.083T_,~/o.7097SG0.6’I’. I J
(A101 1
T Mwt “/.’ Tsowt x and TIOO~~ z are the temperatures in K at
PCi = z xj MW, Py c xj MW, 6413)
which SO,80 and 100 wt “/0 were distilled off. SC is the specific i
j ’ j
gravity of the TBP sample which roughly corresponds to the
C ,+ fraction of the total mixture. wi = Cx,MWjw,
The specific gravities of the subfractions ofthe TBP residue i ZxjMW, (Al4)
j ’ j
are obtained by assuming a logarithmic dependence of SC
where i is a group of carbon number fractions containing, for
against carbon number. For the boiling points, the values of
Katz and Firoozabadi (1978) are used up to Cd5. For gas example, C7-C9. CL o-C a61etc. Indexj runs from the lowest to
the highest carbon number within a group i. For the C,,
condensates, the relation
carbon number fractions, P,.. Tci and wj in eqs (A12)-(A 14)
T,(K) = 97.58 MW0.“23 SG0.04609 (All) are computed using eqs (Alg(A4).